JPH0233399A - Water-resistant paper and production thereof - Google Patents
Water-resistant paper and production thereofInfo
- Publication number
- JPH0233399A JPH0233399A JP1020300A JP2030089A JPH0233399A JP H0233399 A JPH0233399 A JP H0233399A JP 1020300 A JP1020300 A JP 1020300A JP 2030089 A JP2030089 A JP 2030089A JP H0233399 A JPH0233399 A JP H0233399A
- Authority
- JP
- Japan
- Prior art keywords
- paper
- layer
- resin layer
- inorganic filler
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title abstract description 8
- 229920005989 resin Polymers 0.000 claims abstract description 46
- 239000011347 resin Substances 0.000 claims abstract description 46
- 239000011256 inorganic filler Substances 0.000 claims abstract description 31
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 31
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 30
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 15
- 238000001125 extrusion Methods 0.000 claims abstract description 9
- 238000010030 laminating Methods 0.000 claims abstract description 9
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 6
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 6
- 229920003002 synthetic resin Polymers 0.000 claims abstract 13
- 239000000057 synthetic resin Substances 0.000 claims abstract 13
- 229920001169 thermoplastic Polymers 0.000 claims abstract 8
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract 8
- -1 polypropylene Polymers 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 8
- 229920001155 polypropylene Polymers 0.000 claims description 7
- 229920005992 thermoplastic resin Polymers 0.000 claims description 7
- 239000004743 Polypropylene Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- 229920013716 polyethylene resin Polymers 0.000 claims description 3
- 238000003475 lamination Methods 0.000 claims description 2
- 239000000654 additive Substances 0.000 abstract description 17
- 230000000996 additive effect Effects 0.000 abstract description 14
- 238000000465 moulding Methods 0.000 abstract description 3
- 230000003068 static effect Effects 0.000 abstract description 3
- 229920000098 polyolefin Polymers 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract 2
- 239000010410 layer Substances 0.000 description 73
- 239000010408 film Substances 0.000 description 9
- 239000001023 inorganic pigment Substances 0.000 description 8
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229920001684 low density polyethylene Polymers 0.000 description 6
- 239000004702 low-density polyethylene Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000003851 corona treatment Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Paper (AREA)
- Laminated Bodies (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は耐水性、筆記性、印刷適性、低帯電性、耐候性
、引裂強度、寸法安定性、及び不透明性に優れた積層耐
水紙に関する。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a laminated waterproof paper that has excellent water resistance, writability, printability, low static charge, weather resistance, tear strength, dimensional stability, and opacity. .
（従来の技術）
紙シートを基材層とし、この表面に二酸化チタン、酸化
亜鉛又は硫化亜鉛の様な無機顔料を含有するポリエチレ
ンをコーティングしてなる２層構造又は両層の中間に無
機顔料不含ポリエチレン層を介在させてなる３層構造の
印画紙用支持体は公知である。(Prior art) A two-layer structure in which a paper sheet is used as a base layer and the surface thereof is coated with polyethylene containing an inorganic pigment such as titanium dioxide, zinc oxide or zinc sulfide, or an inorganic pigment-free structure is formed between the two layers. A support for photographic paper having a three-layer structure with a polyethylene-containing layer interposed therebetween is known.
これらの積層紙においては、無機顔料によって樹脂層の
不透明化が実現されたことでも充分に実用性付与は達成
されている。しかし、更に高度の要求に対しては、両層
の中間に無機顔料不含の樹脂層を介在させた３層以上と
することが好ましい。In these laminated papers, the resin layer is made opaque by the inorganic pigment, and practicality has been sufficiently achieved. However, for more advanced requirements, it is preferable to use three or more layers with an inorganic pigment-free resin layer interposed between the two layers.
この３層積層紙は無機顔料含有による樹脂層の不透明化
を果たすと共に、無機顔料含有によって生ずる紙基材層
表面と樹脂層との間の接着力低下を防ぐ為に顔料不含樹
脂層を介在させることによって解決したものとされてい
る。また、上記の印画紙用支持体において、紙基材層と
無機顔料含有ポリエチレン層との間に無機顔料不含のポ
リエチレン層を設けたものも公知である。This three-layer laminated paper has an inorganic pigment that makes the resin layer opaque, and a pigment-free resin layer that is interposed to prevent the adhesive strength between the paper base layer surface and the resin layer from decreasing due to the inorganic pigment content. It is said that the problem was solved by doing so. Furthermore, in the above-mentioned support for photographic paper, one in which a polyethylene layer containing no inorganic pigment is provided between the paper base layer and the inorganic pigment-containing polyethylene layer is also known.
（発明が解決しようとする課題）
上記した印画紙用支持体で１よ、微細な写真画像を焼付
ける為の印画紙表面を平滑にする為に紙の表面にポリエ
チレン樹脂層を積層しているが、樹脂層を設けた結果、
支持体表面の透明化が生じた。(Problems to be Solved by the Invention) In the above-mentioned support for photographic paper, a polyethylene resin layer is laminated on the surface of the paper in order to smooth the surface of the photographic paper for printing minute photographic images. However, as a result of providing a resin layer,
Transparency of the support surface occurred.
そこで、樹脂層中に顔料を含有させて白色のバックグラ
ウンドを形成し、明瞭な写真画像が獲られる様にしてい
る。つまり、写真用支持体においては、表面のポリエチ
レン樹脂層中に無機顔料を配合することが望ましいが、
その反面、無機顔料の配合によって樹脂層表面の平滑性
を損なうようなことがあってはならない。この関係から
、配合量が制約されることになり、実用的には７重量％
程度が限界であるとされている。Therefore, a pigment is included in the resin layer to form a white background so that a clear photographic image can be obtained. In other words, in photographic supports, it is desirable to incorporate inorganic pigments into the polyethylene resin layer on the surface;
On the other hand, the blending of inorganic pigments must not impair the smoothness of the resin layer surface. Due to this relationship, the amount of compounding is restricted, and practically 7% by weight.
It is said that there is a limit to the extent of
これに対して、本発明に係わる積層耐水紙は印刷適性、
筆記性を備えていることを必要とする。In contrast, the laminated waterproof paper according to the present invention has excellent printability and
Must be writable.
その為には積層耐水紙の表面には適度の粗さが必要とさ
れることから、写真用支持体の様な７重量％程度の配合
量では表面粗さが不足して、水性又は油性の印刷インキ
、或は筆記用の水性インキの定着、乾燥に支障を来す。For this purpose, the surface of the laminated waterproof paper needs to have an appropriate level of roughness, so if the amount is about 7% by weight, as is the case with photographic supports, the surface roughness will be insufficient, and water-based or oil-based It interferes with the fixing and drying of printing ink or water-based ink for writing.
また、ボールペンや鉛筆による筆記を試みても、平滑な
フィルムそのものと同様に実質的に筆記不可能という不
都合を生ずる。Furthermore, even if one attempts to write with a ballpoint pen or pencil, the problem arises that it is virtually impossible to write on the film, just as with the smooth film itself.
本発明は第１の目的として上記の従来技術上の問題を解
決する手段を提供し、次に第２の目的として印画紙用支
持体で不透明化に使われる二酸化チタン又は酸化亜鉛を
樹脂層中に多量に配合して、も樹脂層の高い帯電性を低
減し得ないことから生ずる欠点、即ちこの様に高い帯電
性を保持したままのシートを多数枚■いて連続的に自動
印刷又は静電自動複写を行なうと、シート間の静電気に
よる相互吸引力によって２枚以上のシートを重ねたまま
給送して紙詰まり等のトラブルの原因となるという問題
を解決する手段を提供することを目的とする。The first object of the present invention is to provide a means for solving the above-mentioned problems in the prior art, and the second object is to incorporate titanium dioxide or zinc oxide, which is used for opacification in photographic paper supports, into a resin layer. The drawback is that even if a large amount is mixed in, the high chargeability of the resin layer cannot be reduced. The purpose of the present invention is to provide a means to solve the problem that when automatic copying is performed, two or more sheets are fed stacked together due to the mutual attraction force caused by static electricity between the sheets, causing problems such as paper jams. do.
（課題を解決する為の手段）
本発明者等は既存の印画紙用支持体である積層紙に類似
しながらも、印刷適性と筆記性とを兼備する積層耐水紙
の開発を進めた結果、印刷画又は筆記面に相当する最外
層の樹脂層中に２０〜８０重量％、好ましくは３０〜５
０重量％の無機充填剤を含有させることが有益であるこ
とを見出した。(Means for Solving the Problems) The present inventors have developed a laminated waterproof paper that is similar to laminated paper, which is an existing support for photographic paper, but has both printability and writability. 20 to 80% by weight, preferably 30 to 5% by weight in the outermost resin layer corresponding to the printed image or writing surface.
It has been found that it is beneficial to include 0% by weight of inorganic filler.
樹脂層中に無機充填剤を２０重量％以上配合させて、厚
さ１０μｍ程度の薄層を製造することは実際上、容易で
はない。各種の試行錯誤によって漸く到達できる技術で
ある。本発明者等の検討も多大の労力と実験とを繰返す
形で行われて来た。In practice, it is not easy to incorporate 20% by weight or more of an inorganic filler into a resin layer and produce a thin layer with a thickness of about 10 μm. This is a technique that can be achieved through various trials and errors. The studies by the present inventors have also involved a great deal of effort and repeated experiments.
本発明の積層体中に配合される無機充填剤、特に比表面
積の比較的大きな部類に属する炭酸カルシウム等の改良
剤では配合前の水分率が重要で、これを特定値以下に規
制することが望まれる。しかも、−旦吸湿した炭酸カル
シウム等を乾燥によって望ましい低水分率へ移行させる
ことは、実際上殆ど不可能といえる。For inorganic fillers to be mixed into the laminate of the present invention, especially modifiers such as calcium carbonate that have a relatively large specific surface area, the moisture content before blending is important, and it is important to regulate this to below a specific value. desired. Furthermore, it is virtually impossible to bring calcium carbonate, etc. that have already absorbed moisture to a desirable low moisture content by drying.
また、使用される無機添加剤の平均粒径は、樹脂層中へ
の分散性並びに無機添加剤が樹脂層に付与する筆記性及
び印刷適性の見地からすれば、通常０．０１〜１０μｍ
１好ましくは０．１〜５μｍ程度とする。In addition, the average particle size of the inorganic additive used is usually 0.01 to 10 μm from the viewpoint of dispersibility in the resin layer and the writability and printability that the inorganic additive imparts to the resin layer.
1 Preferably, it is about 0.1 to 5 μm.
更に、無機添加剤の属性として比表面積及び吸油量が挙
げられる。例えば、二酸化チタンにおいては、ルチル型
であって比表面積１〜５０ｒｔｆ／ｇ。Further, attributes of the inorganic additive include specific surface area and oil absorption. For example, titanium dioxide is of rutile type and has a specific surface area of 1 to 50 rtf/g.
吸油量１０〜５０ｍｌ／ １００ ｇ、炭酸カルシウム
±おいては、平均粒径０．５〜１０μｍ１比表面積０．
５〜７０Ｍ／ｇ、好ましくは１〜３０イ／ｇ（ＢＥＴ法
）、吸油ｆｆ１５〜５０ｍｌ／１００ ｇ、好ましくは
１０〜４０ｍ１／１００ｇとし、重質であることが好ま
しい。Oil absorption: 10-50 ml/100 g, calcium carbonate ±, average particle size: 0.5-10 μm, specific surface area: 0.
It is preferably heavy, with an oil absorption of 5 to 70 M/g, preferably 1 to 30 m/g (BET method), and an oil absorption ff of 15 to 50 ml/100 g, preferably 10 to 40 ml/100 g.
また、他の有効な無機フィラーとしては、タルク、クレ
ー、カオリン、硫酸バリウム、炭酸カルシウム、ケイ酸
カルシウム、炭酸マグネシウム、酸化チタン、酸化亜鉛
、酸化マグネシウム、酸化ケイ素、ケイソウ土、磁性酸
化鉄等、およびこれらの混合物が挙げられる。Other effective inorganic fillers include talc, clay, kaolin, barium sulfate, calcium carbonate, calcium silicate, magnesium carbonate, titanium oxide, zinc oxide, magnesium oxide, silicon oxide, diatomaceous earth, magnetic iron oxide, etc. and mixtures thereof.
なお、カーボンブラック、フェノール樹脂、メラミン樹
脂、尿素樹脂等の有機フィラーを少量混合しても良く、
さらに、フィラーの分散性を向上させる補助手段として
脂肪酸塩、粘着付与剤、親水化ポリオレフィンワックス
等を適宜加えることや、それらでフィラーの表面処理を
行なうことも可能である。In addition, a small amount of organic filler such as carbon black, phenol resin, melamine resin, urea resin, etc. may be mixed.
Furthermore, it is also possible to appropriately add fatty acid salts, tackifiers, hydrophilized polyolefin wax, etc. as auxiliary means for improving the dispersibility of the filler, or to perform surface treatment of the filler with them.
上記無機添加剤が樹脂層中に２０重量％以上という高配
合でありながらも厚さ２０μｍ以下という薄膜に成形さ
れ得るには、該無機添加剤の水分率を５００ ＋１ｔｌ
１１以下に規制することが好ましい。In order to be able to form a thin film with a thickness of 20 μm or less even though the inorganic additive has a high content of 20% by weight or more in the resin layer, the moisture content of the inorganic additive must be 500 + 1 tl.
It is preferable to restrict it to 11 or less.
本発明の積層紙を製造する為に樹脂層を形成するオレフ
ィン系熱可塑性樹脂としては、エチレン系樹脂、プロピ
レン系樹脂及びポリエステル樹脂が好ましい。As the olefin thermoplastic resin forming the resin layer for producing the laminated paper of the present invention, ethylene resin, propylene resin and polyester resin are preferable.
ここでオレフィン系樹脂とは１−オレフィンの単独重合
体に限らず、１−オレフィン相互の共重合体でも、１−
オレフィンと共重合可能な他の単量体例えば酢酸ビニル
、アクリル酸エチル、メタクリル酸メチル等を少量含有
する共重合体でも良い。異種の重合体又は共重合体の組
成物も勿論包含する。Here, the olefin resin is not limited to a homopolymer of 1-olefins, but also a copolymer of 1-olefins.
A copolymer containing a small amount of other monomers copolymerizable with the olefin, such as vinyl acetate, ethyl acrylate, methyl methacrylate, etc., may also be used. Of course, compositions of different polymers or copolymers are also included.
（１）エチレン系熱可塑性樹脂としては、メルトフロー
レート［ＭＦＲ（１９０℃）］ ３〜２０ｇ／ １０ｍ
１ｎ 、溶融張力（＝メルトテンション、１９０℃、押
出機オリフィスのＬ／Ｄ＝３．８、押出速度１５關／＋
ｎｉｎ、引取速度１５ｍ／ｎ＋１ｎ）０．３〜ｌ１ｇで
あるものが好ましい。(1) The ethylene thermoplastic resin has a melt flow rate [MFR (190°C)] of 3 to 20 g/10 m
1n, melt tension (=melt tension, 190°C, extruder orifice L/D = 3.8, extrusion speed 15/+
nin, take-up speed 15m/n+1n) 0.3 to l1g is preferable.
（２）プロピレン系熱可塑性樹脂としては、メルトフロ
ーレート ［ＭＦ Ｒ（２３０’Ｃ） ］ １．５〜
５０ ｇ／ １０ｍ１ｎ 、溶融張力（２３０℃、押出
機オリフィスのＬ／Ｄ＝３．８、押出速度１５ｍｍ／ｍ
１ｎ１引取速度１５ｍ／ｍｉ口）０．３〜３．３である
ものが好ましい。(2) The propylene thermoplastic resin has a melt flow rate [MF R (230'C)] of 1.5 to
50 g/10 m1n, melt tension (230°C, extruder orifice L/D = 3.8, extrusion speed 15 mm/m
1n1 take-up speed 15 m/mi) is preferably 0.3 to 3.3.
本発明の積層紙の製造法としては、紙基材層の少くとも
１面に無機添加剤不含のポリオレフィン樹脂層をＴダイ
成膜機から押出成形し、更にその上面に、別途無機添加
剤含有ポリオレフィン樹脂層をＴダイ成膜機から押出成
形しながら３者を積層接合する方法が好ましい。The method for producing the laminated paper of the present invention involves extruding a polyolefin resin layer containing no inorganic additives on at least one side of the paper base layer using a T-die film forming machine, and then adding a separate inorganic additive to the upper surface of the polyolefin resin layer. A method of laminating and bonding the three components while extruding the containing polyolefin resin layer from a T-die film forming machine is preferred.
ここで各樹脂層の厚さは無機添加剤含有層において通常
３μｍ以上、好ましくは５〜１０μｍ１紙基材に接する
層において通常５μｍ以上、好ましくは５〜１５μｍと
する。Here, the thickness of each resin layer is usually 3 μm or more, preferably 5 to 10 μm in the inorganic additive-containing layer, and usually 5 μm or more, preferably 5 to 15 μm in the layer in contact with the paper base material.
なお、最外層と紙に接する樹脂層とは同種の材料、例え
ば低密度エチレン系樹脂同志、高密度エチレン系樹脂同
志、プロピレン系重合体同志及び１−ブテン系重合体同
志等の組合せ系であることが好ましい。これら重合体が
２種以上の重合体の組成物からなる場合にも、各層の構
成重合体の内訳及び両者の配合比率が両層間で同一であ
るものが包含されている。The outermost layer and the resin layer in contact with the paper are made of the same type of material, such as a combination of low-density ethylene resins, high-density ethylene resins, propylene polymers, and 1-butene polymers. It is preferable. Even when these polymers are composed of a composition of two or more types of polymers, it is included that the breakdown of the constituent polymers of each layer and the blending ratio of both layers are the same between the two layers.
本発明の積層紙の製造法としては、紙基材層の少くとも
１表面に無機添加剤を含むオレフィン系熱可塑性樹脂層
をＴダイ成膜機から押出成形しながら積層接着する方法
が好ましい。この方法によって得られる積層紙は通常の
使用には十分に耐える程度の層間接着力を備えている。As a method for manufacturing the laminated paper of the present invention, a method of laminating and adhering an olefinic thermoplastic resin layer containing an inorganic additive on at least one surface of a paper base layer while extrusion molding from a T-die film forming machine is preferable. The laminated paper obtained by this method has interlayer adhesion strength sufficient to withstand normal use.
更に好ましい製造法としては次記する様に紙基材層と無
機添加剤含有樹脂層との中間に無機添加剤不含の樹脂層
を介在させる方法を挙げることができる。この方法によ
れば、無機添加剤層の厚さを低い側へ移しても膜切れ等
の発生を抑えて安定な成形を行なうことが一層容易にな
る。A more preferred manufacturing method is a method in which a resin layer containing no inorganic additive is interposed between the paper base layer and the inorganic additive-containing resin layer, as described below. According to this method, even if the thickness of the inorganic additive layer is reduced, it becomes easier to suppress the occurrence of film breakage and perform stable molding.
勿論、紙基材層の両面に直接に無機添加剤配合樹脂層を
積層接着してもよく、紙基材層の両面に無機添加剤不含
樹脂層を積層した後、又は積層と同時併行で該樹脂層の
表面に更に無機添加剤含有樹脂層を積層接着しても差支
えない。Of course, the inorganic additive-containing resin layer may be laminated and bonded directly on both sides of the paper base layer, or after laminating the inorganic additive-free resin layer on both sides of the paper base layer, or simultaneously with the lamination. There is no problem in further laminating and adhering a resin layer containing an inorganic additive on the surface of the resin layer.
更に、紙との接着性を高める為に押出し塗工前の紙基材
層の表面にフレーム（火炎）処理、コロナ放電処理及び
予熱処理又は積層されるべき樹脂層の紙と接すべき面に
オゾン処理等の処理を施すと、低温で両層間に接着性を
付与することが望ましい。その結果、樹脂からの目ヤニ
発生頻度減少及び樹脂の劣化や引裂強度低下の防止を実
現できる。Furthermore, in order to improve adhesion to paper, the surface of the paper base layer before extrusion coating is subjected to flame treatment, corona discharge treatment, and preheating treatment, or the surface of the resin layer to be laminated that is in contact with paper is treated with flame treatment, corona discharge treatment, and preheating treatment. It is desirable that treatment such as ozone treatment imparts adhesion between both layers at low temperatures. As a result, it is possible to reduce the frequency of occurrence of eye stain from the resin and to prevent resin deterioration and tear strength reduction.
紙基材層に樹脂層を積層することによって得られた耐水
紙の表面の粗さは、無機添加剤の含量、平均粒径、最外
層の膜厚を適当に選定することによって変えることがで
きるが、中でもラミネーターのクーリングロールパター
ンを変えて製品の表面をマット調に仕上げることによっ
て、鉛筆筆記性を上げることができる。ここで“マット
調”とは６０’入射角におけるグロスが３０％以下であ
ることをいう。更に必要あれば、帯電防止剤、インキ接
着改良剤、紫外線吸収剤等を少くとも樹脂の１層中に配
合又は最外層表面に塗布してもよい。The surface roughness of waterproof paper obtained by laminating a resin layer on a paper base layer can be changed by appropriately selecting the content of inorganic additives, average particle size, and thickness of the outermost layer. However, pencil writing ability can be improved by changing the cooling roll pattern of the laminator to give the product a matte finish. Here, "matte" means that the gloss at a 60' incident angle is 30% or less. Furthermore, if necessary, an antistatic agent, an ink adhesion improver, an ultraviolet absorber, etc. may be incorporated into at least one layer of the resin or coated on the surface of the outermost layer.
本発明においては、無機添加剤として特定種類のものを
組合せることによって、帯電性の実質的増加を伴うこと
なしに樹脂層に筆記性及び印刷適性を付与することがで
きる。In the present invention, by combining specific types of inorganic additives, writability and printability can be imparted to the resin layer without substantially increasing chargeability.
特に、最外層の熱可塑性樹脂層に無機充填剤３０〜５０
重量％が含有され、更にその無機充填剤が主として炭酸
カルシウムと二酸化チタンとからなり、両者の比率が９
９：１〜５５ 二４５、好ましくは８０ ： ２０〜６
０ ： ４０であることが最も望ましい。このような構
成の場合、最外層の表面抵抗値はＩ Ｘ １０ ”〜９
Ｘ１０”Ωとなり、筆記性、印刷適性ともに極めて良好
である。In particular, the outermost thermoplastic resin layer contains 30 to 50 inorganic fillers.
% by weight, and the inorganic filler mainly consists of calcium carbonate and titanium dioxide, and the ratio of both is 9.
9:1-55 245, preferably 80:20-6
A ratio of 0:40 is most desirable. In such a configuration, the surface resistance value of the outermost layer is I x 10''~9
X10''Ω, and both the writability and printability are extremely good.
なお、本発明の積層体における表面抵抗は２３℃、相対
湿度（ＲＨ）５Ｑ％において測定した値である。Note that the surface resistance of the laminate of the present invention is a value measured at 23° C. and a relative humidity (RH) of 5Q%.
（実施例） 以下に本発明の実施例及びその比較例を示す。(Example) Examples of the present invention and comparative examples thereof are shown below.
なお、実施例および比較例で得られた積層耐水紙につい
て、下記の物性を測定し、その結果を表１〜２に示した
。The following physical properties were measured for the laminated waterproof papers obtained in Examples and Comparative Examples, and the results are shown in Tables 1 and 2.
［測定物性］ ［測定方法］厚 さ
：ＪＩＳ Ｐ−８１１８不透明度 ：ＪＩ
Ｓ Ｐ−８１３８浸水伸度 ： Ｊ、ＴＡＰＰ ｒ
Ｎａ２７耐湿表面摩耗＋ＪＩＳ Ｐ−８１３６筆 記
性 ゛：硬度２Ｂの鉛筆を使用して、一定の圧力下で
鉛筆試験を行った。[Measurement properties] [Measurement method] Thickness
:JIS P-8118 Opacity :JI
SP-8138 Water immersion elongation: J, TAPP r
Na27 moisture resistance surface abrasion + JIS P-8136 writing property ゛: A pencil test was conducted under a constant pressure using a pencil with a hardness of 2B.
判定基準は次の通りである。The judgment criteria are as follows.
◎ 非常に良く書ける Ｏ 良く書ける。◎ Can write very well O: Can write well.
× 全然書けない。× I can't write at all.
６） 表面抵抗値 二用日電気■製ＭｏｄｅＩ Ｐ−６
０１゜ＭＥ−３０を使用し、２３℃Ｘ６０％ＲＨ（７）
雰囲気中で測定した。6) Surface resistance value Model I P-6 manufactured by Nichidenki ■
Using 01°ME-30, 23°C x 60%RH (7)
Measured in atmosphere.
７） 印刷適性 ：ローランド・オフセット平版印刷
機（２０２Ｂ）を使用した。印刷用紙の寸法は２９７Ｘ
４２０ｍｍ （Ａ３）であり、給紙速度は８０００枚／
時で印刷室の雰囲気は２０℃×５０％ＲＨであった。尚
、インキは大日本インキ化学工業■ｐｏｐ−ｓを使用し
た。7) Printability: A Roland offset lithographic printing machine (202B) was used. The dimensions of the printing paper are 297X
420mm (A3), paper feeding speed is 8000 sheets/
The atmosphere in the printing room was 20° C. x 50% RH. Incidentally, the ink used was Dainippon Ink Chemical Industry ■ POP-S.
（実施例１）
低密度ポリエチレン（ＭＦＲｌ １ ｇ／ｌ ０分、密
度０．９１６ ｇ／ａｍ３、メルトテンション１．３ｇ
）７５重ｍｍを溶融状態として、これに炭酸カルシウム
（平均粒径２μｍ）と酸化チタン（平均粒径０．２μｍ
）を重量比で９５＝５の割合いで２５重七％を添加混合
した。この混合物をＴダイより２９０℃の温度で押出し
、溶融膜の紙と接着させる面にオゾン含有空気を吹付け
ながら、厚さ６０μｍ、幅５００ｍｍの耐水複写紙の両
面に積層し、積層耐水紙を得た。この時の、オゾン処理
の条件は、溶融膜の積層速度Ｌｏｏｍ／分、エアギャッ
プ１３０ｍｍ、オゾン濃度４０ｇ／ｍ’、オゾン流ｆｆ
１２ｍ’／ｈであった。なお、この実施例で使用した耐
水複写紙は、坪Ｗｋ４８ｇ／ｍ３の上質紙を原紙として
、澱粉／ポリビニルアルコール＝８０／２０の塗工液を
塗布量１〜２ｇ／ｍ’でサイズプレス塗工したステキヒ
トサイズ度３０秒の、ゼログラフコピー用紙である。(Example 1) Low density polyethylene (MFRl 1 g/l 0 min, density 0.916 g/am3, melt tension 1.3 g
) 75 weight mm in a molten state, calcium carbonate (average particle size 2 μm) and titanium oxide (average particle size 0.2 μm
) were added and mixed in a weight ratio of 95=5 in an amount of 25 weight and 7%. This mixture was extruded through a T-die at a temperature of 290°C, and while blowing ozone-containing air to the surface of the molten film to be adhered to the paper, it was laminated on both sides of waterproof copying paper with a thickness of 60 μm and a width of 500 mm to form a laminated waterproof paper. Obtained. The ozone treatment conditions at this time were: molten film stacking speed Loom/min, air gap 130 mm, ozone concentration 40 g/m', ozone flow ff
It was 12 m'/h. The waterproof copying paper used in this example was size press coated with a coating solution of starch/polyvinyl alcohol = 80/20 at a coating amount of 1 to 2 g/m' on a high-quality paper of tsubo Wk 48 g/m3 as a base paper. This is xerographic copy paper with a Steckicht size of 30 seconds.
（実施例２）
実施例１において、炭酸カルシウムと酸化チタンとの配
合割合を８０ ： ２０とし、これらの無機フィラーの
含有量を低密度ポリエチレン７０重量％に対して３０重
量％とじた以外は、同様にして積層耐水紙を得た。(Example 2) In Example 1, the blending ratio of calcium carbonate and titanium oxide was 80:20, and the content of these inorganic fillers was 30% by weight relative to 70% by weight of low density polyethylene. Laminated waterproof paper was obtained in the same manner.
（実施例３）
実施例１で用いた低密度ポリエチレン２５重量％を溶融
状態として、これに炭酸カルシウムと酸化チタンを重量
比で６０：４０の割合いで７５重量％を添加混合した。(Example 3) 25% by weight of the low density polyethylene used in Example 1 was brought into a molten state, and 75% by weight of calcium carbonate and titanium oxide were added and mixed at a weight ratio of 60:40.
これとは別に、上記の低密度ポリエチレンの無機フィラ
ーを含有しないものを用意し、この無機フィラーを含有
しない樹脂を紙に接する下側層とし、先の無機フィラー
含有の樹脂を最外層として、共押出しＴダイより２９０
℃の温度で、実施例１と同じ耐水複写紙の両面に押出し
て圧着し、積層耐水紙を得た。Separately, prepare the above-mentioned low-density polyethylene that does not contain inorganic filler, use the resin that does not contain inorganic filler as the lower layer that contacts the paper, and use the resin that contains the inorganic filler as the outermost layer. 290 from extrusion T die
The mixture was extruded and pressure-bonded onto both sides of the same waterproof copying paper as in Example 1 at a temperature of 1°C to obtain a laminated waterproof paper.
（実施例４）
ポリプロピＬ／：／ （ＭＦＲ２５ｇ／１０分、密度０
．９１ｇ／ｃｍ３、メルトテンション０．５ｇ）６５重
量％を溶融状態として、これに炭酸カルシウムと酸化チ
タンを重量比で９５＝５の割合いで３５重量％を添加混
合した。これとは別に、上記のポリプロピレンの無機フ
ィラーを含有しないものを用意し、この無機フィラーを
含有しない樹脂を紙に接する下側層とし、先の無機フィ
ラー含有の樹脂を最外層として、共押出しＴダイより２
９０℃の温度で、実施例１と同じ耐水複写紙の両面に押
出して圧着し、積層耐水紙を得た。なお、共押出しに際
して、紙に接する下側層となる溶融樹脂膜の紙と接着さ
せる面には実施例１と同様のオゾン処理を施した。(Example 4) Polypropy L/:/ (MFR25g/10min, density 0
．． 91 g/cm3, melt tension 0.5 g) was brought into a molten state, and 35% by weight of calcium carbonate and titanium oxide were added and mixed in a weight ratio of 95=5. Separately, prepare the above-mentioned polypropylene that does not contain an inorganic filler, use this inorganic filler-free resin as the lower layer in contact with the paper, and co-extrude the inorganic filler-containing resin as the outermost layer. 2 from die
At a temperature of 90° C., the mixture was extruded and pressed onto both sides of the same waterproof copying paper as in Example 1 to obtain a laminated waterproof paper. Note that during coextrusion, the same ozone treatment as in Example 1 was applied to the surface of the molten resin film, which was the lower layer in contact with the paper, and was to be adhered to the paper.
（実施例５）
実施例４において、炭酸カルシウムと酸化チタンの他に
シリカを加え、その配合割合を８０＝１０：１０とし、
これらの無機フィラーの含有量をポリプロピレン５５重
量％に対して４５重量％とし、上質紙（坪量７０ｇ／ｍ
３）を紙基材層とした以外は、同様１こして積層耐水紙
を得た。(Example 5) In Example 4, silica was added in addition to calcium carbonate and titanium oxide, and the blending ratio was 80 = 10:10,
The content of these inorganic fillers was 45% by weight based on 55% by weight of polypropylene,
A laminated waterproof paper was obtained in the same manner as above except that 3) was used as the paper base layer.
（実施例６）
実施例５において、無機フィラーとしてタルク（平均粒
径０８μｍ）を用いてポリプロピレン７０重量％に対し
て３０重量％配合し、無機フィラーを含まない下側樹脂
層なしに、Ｔダイより２９０℃の温度で押出し、オゾン
処理を施しながら、上質紙の両面に積層し、積層耐水紙
を得た。(Example 6) In Example 5, talc (average particle size 08 μm) was used as an inorganic filler and was blended at 30% by weight with respect to 70% by weight of polypropylene, and a T-die was formed without a lower resin layer containing no inorganic filler. The mixture was extruded at a temperature of 290° C. and laminated on both sides of high-quality paper while being subjected to ozone treatment to obtain a laminated waterproof paper.
（実施例７）
実施例５において、無機フィラーとして、炭酸カルシウ
ムを用いてポリプロピレン７０重量％に対して３０重量
％配合した以外は同様にして、積層耐水紙を得た。(Example 7) A laminated waterproof paper was obtained in the same manner as in Example 5, except that calcium carbonate was used as an inorganic filler and was blended in an amount of 30% by weight based on 70% by weight of polypropylene.
（比較例１）
実施例１において、無機フィラーを含有しない低密度ポ
リエチレンを使用した以外は同様にして、積層紙を得た
。(Comparative Example 1) A laminated paper was obtained in the same manner as in Example 1 except that low-density polyethylene containing no inorganic filler was used.
（比較例２）
実施例６において、無機フィラーを含有しないポリプロ
ピレンを使用した以外は同様にして、積層紙を得た。(Comparative Example 2) A laminated paper was obtained in the same manner as in Example 6 except that polypropylene containing no inorganic filler was used.
（比較例３及び４）
上記実施例で使用した耐水複写紙と上質紙を、そのまま
用いた。(Comparative Examples 3 and 4) The waterproof copying paper and high-quality paper used in the above examples were used as they were.
（実施例８．９及び１０）
実施例４において、無機フィラーとして使用した炭酸カ
ルシウムと酸化チタンの配合８１１合を表２に示す如く
各種変化させて、耐水複写紙を１尋た。(Examples 8, 9 and 10) In Example 4, the combination of calcium carbonate and titanium oxide used as the inorganic filler was varied in various ways as shown in Table 2, and one sheet of waterproof copying paper was prepared.
（実施例１１．１２．１３及び比較例５）実施例３にお
いて、低密度ポリエチレン番二対する無機フィラーの配
合量を表２に示す如く各種変化させて、耐水複写紙を得
た。(Examples 11, 12, 13 and Comparative Example 5) In Example 3, the amount of inorganic filler added to low density polyethylene No. 2 was varied as shown in Table 2 to obtain waterproof copying paper.
Claims (7)
可塑性合成樹脂が積層されており、その合成樹脂層の中
の少なくとも最外層の合成樹脂層に無機充填剤２０〜８
０重量％が含有されている印刷性良好で低帯電性の積層
耐水紙。(1) Paper is used as a base material layer, at least one layer of thermoplastic synthetic resin is laminated on the surface thereof, and at least the outermost synthetic resin layer of the synthetic resin layer contains an inorganic filler of 20 to 8
Laminated waterproof paper with good printability and low chargeability, containing 0% by weight.
ない熱可塑性合成樹脂層が少なくとも１層積層され、更
にその合成樹脂層の表面に無機充填剤２０〜８０重量％
を含有する熱可塑性合成樹脂層が少なくとも１層積層さ
れてなる印刷性良好で低帯電性の積層耐水紙。(2) Paper is used as a base layer, and at least one thermoplastic synthetic resin layer containing no inorganic filler is laminated on the surface thereof, and the surface of the synthetic resin layer is further coated with 20 to 80% by weight of inorganic filler.
A laminated waterproof paper with good printability and low chargeability, which is formed by laminating at least one thermoplastic synthetic resin layer containing:
填剤３０〜５０重量％が含有され、更にその無機充填剤
が主として炭酸カルシウムと二酸化チタンとからなり、
且つ両者の比率が重量基準で８０：２０〜６０：４０で
あることを特徴とする請求項１又は２に記載の積層耐水
紙。(3) 30 to 50% by weight of an inorganic filler is contained in at least the outermost thermoplastic synthetic resin layer, and the inorganic filler mainly consists of calcium carbonate and titanium dioxide,
The laminated waterproof paper according to claim 1 or 2, wherein the ratio of both is 80:20 to 60:40 on a weight basis.
ルトフローレート［ＭＦＲ（２３０℃）］１５〜５０ｇ
／１０ｍｉｎ、溶融張力［（２３０℃）、Ｌ／Ｄ＝３．
８、押出し速度１５ｍｍ／ｍｉｎ、引き取り速度１５ｍ
／ｍｉｎ］０．３〜３．３ｇであることを特徴とする請
求項１ないし３の何れかに記載の積層耐水紙。(4) The thermoplastic synthetic resin is a polypropylene resin, and the melt flow rate [MFR (230°C)] is 15 to 50 g.
/10min, melt tension [(230°C), L/D=3.
8. Extrusion speed 15mm/min, take-off speed 15m
4. The laminated waterproof paper according to any one of claims 1 to 3, wherein the amount is 0.3 to 3.3 g/min].
トフローレート［ＭＦＲ（１９０℃）］３〜２０ｇ／１
０ｍｉｎ、溶融張力（１９０℃、Ｌ／Ｄ＝３．８、押出
し速度１５ｍｍ／ｍｉｎ、引き取り速度１５ｍ／ｍｉｎ
）０．３〜１１ｇであることを特徴とする請求項１ない
し４の何れかに記載の積層耐水紙。(5) The thermoplastic synthetic resin is a polyethylene resin, and the melt flow rate [MFR (190°C)] is 3 to 20 g/1.
0min, melt tension (190°C, L/D=3.8, extrusion speed 15mm/min, withdrawal speed 15m/min
) The laminated waterproof paper according to any one of claims 1 to 4, wherein the weight is 0.3 to 11 g.
状態の熱可塑性樹脂と、無機フィラーを含有させない熱
可塑性樹脂とを、Ｔダイ内で後者の樹脂が紙基材層の表
面に接する側に位置するように積層しながらＴダイから
２層のフィルム状に押し出して紙基材の表面に積層接着
することを特徴とする積層耐水紙の製造方法。(6) A molten thermoplastic resin containing 20 to 80% by weight of an inorganic filler and a thermoplastic resin containing no inorganic filler are placed in a T-die on the side where the latter resin is in contact with the surface of the paper base layer. 1. A method for producing laminated waterproof paper, which comprises extruding it from a T-die into a two-layer film while laminating the paper so that the paper is positioned at the top of the paper, and then laminating and adhering the two-layered film to the surface of a paper base material.
しないオレフィン系樹脂層を少なくとも１層溶融状態で
押出し積層し、次いでその樹脂層の表面に組成物基準で
２０〜８０重量％でしかも炭酸カルシウム９９〜５５重
量％と酸化チタン１〜４５重量％とから主としてなる無
機充填剤を含有するオレフィン系樹脂層を少なくとも１
層溶融状態で押出し積層することを特徴とする積層耐水
紙の製造方法。(7) Using paper as a base layer, at least one olefin resin layer containing no inorganic filler is extruded and laminated in a molten state on the surface thereof, and then 20 to 80% by weight of the composition is applied to the surface of the resin layer. Moreover, at least one olefinic resin layer containing an inorganic filler mainly composed of 99 to 55% by weight of calcium carbonate and 1 to 45% by weight of titanium oxide is used.
A method for producing laminated waterproof paper characterized by extrusion lamination in a molten state.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1020300A JP2763011B2 (en) | 1988-01-28 | 1989-01-30 | Water resistant paper and method for producing the same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63-18374 | 1988-01-28 | ||
| JP1837488 | 1988-01-28 | ||
| JP1020300A JP2763011B2 (en) | 1988-01-28 | 1989-01-30 | Water resistant paper and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0233399A true JPH0233399A (en) | 1990-02-02 |
| JP2763011B2 JP2763011B2 (en) | 1998-06-11 |
Family
ID=26355058
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1020300A Expired - Lifetime JP2763011B2 (en) | 1988-01-28 | 1989-01-30 | Water resistant paper and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2763011B2 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4302210C2 (en) * | 1992-01-27 | 2001-02-22 | Mitsubishi Paper Mills Ltd | Resin-coated paper and its use |
| US7749591B2 (en) | 2004-09-30 | 2010-07-06 | Nippon Paper Industries Co., Ltd. | Laminated sheet |
| JP2010536677A (en) * | 2007-08-18 | 2010-12-02 | スマート プラネット テクノロジーズ インコーポレーテッド | Flexible packaging composite material |
| JP2012512073A (en) * | 2008-12-15 | 2012-05-31 | ヒューレット−パッカード デベロップメント カンパニー エル．ピー． | Things that can be imaged |
| JP2012517360A (en) * | 2009-02-09 | 2012-08-02 | スマート プラネット テクノロジーズ インコーポレイテッド | COMPOSITE MATERIAL FOR PACKAGING ARTICLE AND METHOD FOR PRODUCING THE SAME |
| US9637866B2 (en) | 2013-03-14 | 2017-05-02 | Smart Planet Technologies, Inc. | Repulpable and recyclable composite packaging articles and related methods |
| JP2017529444A (en) * | 2014-09-24 | 2017-10-05 | ザ ケマーズ カンパニー ティーティー リミテッド ライアビリティ カンパニー | Materials with enhanced protection of photosensitive entities |
| US10633799B2 (en) | 2013-03-14 | 2020-04-28 | Smart Planet Technologies, Inc. | Composite structures for packaging articles and related methods |
| WO2022176437A1 (en) * | 2021-02-19 | 2022-08-25 | 三井化学株式会社 | Resin composition and use thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4930446A (en) * | 1972-03-02 | 1974-03-18 | ||
| JPS632800U (en) * | 1986-06-24 | 1988-01-09 |
-
1989
- 1989-01-30 JP JP1020300A patent/JP2763011B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4930446A (en) * | 1972-03-02 | 1974-03-18 | ||
| JPS632800U (en) * | 1986-06-24 | 1988-01-09 |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4302210C2 (en) * | 1992-01-27 | 2001-02-22 | Mitsubishi Paper Mills Ltd | Resin-coated paper and its use |
| US7749591B2 (en) | 2004-09-30 | 2010-07-06 | Nippon Paper Industries Co., Ltd. | Laminated sheet |
| JP2010536677A (en) * | 2007-08-18 | 2010-12-02 | スマート プラネット テクノロジーズ インコーポレーテッド | Flexible packaging composite material |
| JP2010536620A (en) * | 2007-08-18 | 2010-12-02 | スマート プラネット テクノロジーズ インコーポレーテッド | COMPOSITE MATERIAL FOR PACKAGING ARTICLE AND METHOD FOR PRODUCING THE SAME |
| US8569411B2 (en) | 2007-08-18 | 2013-10-29 | Smart Planet Technologies, Inc. | Flexible packaging composites |
| US9346238B2 (en) | 2007-08-18 | 2016-05-24 | Smart Planet Technologies, Inc. | Flexible packaging composites |
| JP2012512073A (en) * | 2008-12-15 | 2012-05-31 | ヒューレット−パッカード デベロップメント カンパニー エル．ピー． | Things that can be imaged |
| JP2012517360A (en) * | 2009-02-09 | 2012-08-02 | スマート プラネット テクノロジーズ インコーポレイテッド | COMPOSITE MATERIAL FOR PACKAGING ARTICLE AND METHOD FOR PRODUCING THE SAME |
| US9637866B2 (en) | 2013-03-14 | 2017-05-02 | Smart Planet Technologies, Inc. | Repulpable and recyclable composite packaging articles and related methods |
| US10421848B2 (en) | 2013-03-14 | 2019-09-24 | Smart Planet Technologies, Inc. | Repulpable and recyclable composite packaging articles and related methods |
| US10633799B2 (en) | 2013-03-14 | 2020-04-28 | Smart Planet Technologies, Inc. | Composite structures for packaging articles and related methods |
| US10822468B2 (en) | 2013-03-14 | 2020-11-03 | Smart Planet Technologies, Inc. | Repulpable and recyclable composite packaging articles and related methods |
| US11466138B2 (en) | 2013-03-14 | 2022-10-11 | Smart Planet Technologies, Inc. | Repulpable and recyclable composite packaging articles and related methods |
| US11479916B2 (en) | 2013-03-14 | 2022-10-25 | Smart Planet Technologies, Inc. | Composite structures for packaging articles and related methods |
| JP2017529444A (en) * | 2014-09-24 | 2017-10-05 | ザ ケマーズ カンパニー ティーティー リミテッド ライアビリティ カンパニー | Materials with enhanced protection of photosensitive entities |
| WO2022176437A1 (en) * | 2021-02-19 | 2022-08-25 | 三井化学株式会社 | Resin composition and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2763011B2 (en) | 1998-06-11 |
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